1,555 research outputs found
Direct nonadiabatic quantum dynamics simulations of the photodissociation of phenol
Gaussian wavepacket methods are becoming popular for the investigation of nonadiabatic molecular dynamics. In the present work, a recently developed efficient algorithm for the Direct Dynamics variational Multi-Configurational Gaussian (DD-vMCG) method has been used to describe the multidimensional photodissociation dynamics of phenol including all degrees of freedom. Full-dimensional quantum dynamic calculations including for the first time six electronic states (1ππ, 11ππ*, 11πσ*, 21πσ*, 21ππ*, 31ππ*), along with a comparison to an existing analytical 4-state model for the potential energy surfaces are presented. Including the fifth singlet excited state is shown to have a significant effect on the nonadiabatic photodissociation of phenol to the phenoxyl radical and hydrogen atom. State population and flux analysis from the DD-vMCG simulations of phenol provided further insights into the decay mechanism, confirming the idea of rapid relaxation to the ground state through the 1ππ/11πσ* conical intersection
Two-dimensional vibronic spectroscopy of molecular aggregates: Trimers, dimers, and monomers
The two-dimensional (2D) vibronic spectroscopy of molecular trimers is studied theoretically. The solution of the time-dependent Schrödinger equation is carried out with the multi-configurational time-dependent Hartree (MCTDH) method which allows for an efficient propagation of the multi-component wave functions. 2D-spectra are calculated for H- and J-type aggregates incorporating one or two vibrational modes for each monomer. In performing calculations for monomer, dimer, and trimer systems, it is documented how the vibronic structure of the 2D-spectrum changes upon aggregation. This is of importance for the characterization of aggregation behavior being influenced by experimental conditions such as temperature or concentration
Improved algorithm for the direct dynamics variational multi-configurational Gaussian method.
The Direct Dynamics variational Multi-Configurational Gaussian (DD-vMCG) method provides a fully quantum mechanical solution to the time-dependent Schrödinger equation for the time evolution of nuclei with potential surfaces calculated on-the-fly using a quantum chemistry program. Initial studies have shown its potential for flexible and accurate simulations of non-adiabatic excited-state molecular dynamics. In this paper, we present developments to the DD-vMCG algorithm that improve both its accuracy and efficiency. First, a new, efficient parallel algorithm to control the DD-vMCG database of quantum chemistry points is presented along with improvements to the Shepard interpolation scheme. Second, the use of symmetry in describing the potential surfaces is introduced along with a new phase convention in the propagation diabatization. Benchmark calculations on the allene radical cation including all degrees of freedom then show that the new scheme is able to produce a consistent non-adiabatic coupling vector field. This new DD-vMCG version thus opens the route for effectively and accurately treating complex chemical systems using quantum dynamics simulations
Neural Dynamics in Parkinsonian Brain:The Boundary Between Synchronized and Nonsynchronized Dynamics
Synchronous oscillatory dynamics is frequently observed in the human brain.
We analyze the fine temporal structure of phase-locking in a realistic network
model and match it with the experimental data from parkinsonian patients. We
show that the experimentally observed intermittent synchrony can be generated
just by moderately increased coupling strength in the basal ganglia circuits
due to the lack of dopamine. Comparison of the experimental and modeling data
suggest that brain activity in Parkinson's disease resides in the large
boundary region between synchronized and nonsynchronized dynamics. Being on the
edge of synchrony may allow for easy formation of transient neuronal
assemblies
Excitations of attractive 1-D bosons: Binding vs. fermionization
The stationary states of few bosons in a one-dimensional harmonic trap are
investigated throughout the crossover from weak to strongly attractive
interactions. For sufficient attraction, three different classes of states
emerge: (i) N-body bound states, (ii) bound states of smaller fragments, and
(iii) gas-like states that fermionize, that is, map to ideal fermions in the
limit of infinite attraction. The two-body correlations and momentum spectra
characteristic of the three classes are discussed, and the results are
illustrated using the soluble two-particle model.Comment: 7 pages, 5 figure
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